Bacteriostatic and fungicidal solution for retarding deterioration and decompositionof organic matter and method of using the same



Patented Dec. 16, 1952 BACTERIOSTATIC AND FUNGICIDAL SOLU- TION FOR RETARDING DETERIORATION AND DECOMPOSITION OF ORGANIC MAT- QTER AND METHOD OF USING THE SAME Lawrence Frandsen, .Seattle, Wash., assignor to Washington Laboratories, Inc., Seattle, Wash, a corporation of Washington No Drawing. Application September 27, 1951, Serial No. 248,650

55 Claims.

' My invention relates to a bacteriostatic and fungicidal solution for retarding deterioration and decomposition by agents such as bacteria and mold of the character which are found causing food spoilage and/or are foundon organic substances.

The invention finds particular application in treating foods, even easily perishable foods, such as fish and shell fish including clams, shrimp, oysters, and crabs, and such shell fish being either in theirraw or cooked state. Also, my invention finds application in the case-of vegetables, as lettuce, cauliflower, celery, kale, carrots and so forth. Also, my invention finds application in preserving common fruit juices, for example, apple, orange and grapefruit. Normally and preferably these products would be treated in their raw state. Likewise, my invention relates to the retarding of bacteria and spore producing mold or fungus growth on the skins of apples, pears, guava fruit, and of citrus fruit, as oranges, lemons, grapefruit and tangerines.

In its broad aspect, my invention'relates to the discovery of the property of fumaric acid when combined with sodium benzoate, or when combined with boric acid, or when combined'with sodium benzoate and boric acid and in each case with water (or in the case of juices, with juices, which, of course,-include Water) to provide an aqueous composition for retarding bacterial and spore producing mold or fungus growth.

My invention is applicable to food which is subject to being spoiled by-bacteria and mold whether in the rawor cooked state.

The above examples are cited by way of illustrationsand not limitations.

As illustrative of the effectiveness of my invention, I have found thata solution of my invention as set-forth hereinafter when applied to mold that has already fully developed on an orange that my'invention operates as a fungicidal agent and causes the mold to dry up and cease further action.

' This application relates to the art .of preserving food'fo which applicant ha heretofore filed applications involving solutions of maleic acid and sodium benzoate, maleic acid and boric acid, and maleic acid, sodium benzoate and boric acid. Fumaric acid is an isomer of maleic acid. This application is a continuation-in-part of the applications filed by me Serial Number 731,561, March 13, 1947, for Composition of Matter and Method ofv Retarding the Decomposition of Food, Serial Number 138,944, January 6, 1950, for A Bacteriostatic and Fungicidal Solution for Retarding Deterioration and Decomposition of Food, and Serial Number 232,068, June. 16, 1951', for A Bacteriostatic and Fungicidal Solu- .2 tion for Retarding Deterioration and Decomposition of Organic Matter.

It will be noted that fumaric and maleic acids are both unsaturated dibasic acids containing four carbon atoms and are isomers of each other.

The preserving of foods presents many problems. In applying chemicals, care must be'taken that the chemicals are such as are not toxic in the concentrations necessary to be employed to obtain eifective action against the food destroying agencies. Also, the chemicals must be of a character as not to aifect the taste and at the same time must be sufficiently potentto negate the action of the agencies operating against the preservation of the food. When freezing or refrigerating temperatures are employed in preserving, then the maintenance of such temperatures is vital as such food readily deteriorates or spoils or is often objectionably affected by even a short temporary thawing or failure of temperature control. At this point is where an eifective preservative compound or agency is of very great importance. In such a situation my antiseptic composition functions to preserve the food until the same is used or refrigerated in a reasonable time.

The purpose of my invention is to provide a new composition of matter formed from water soluble chemicals, 'fumaric acid, sodium benzoate, and boric acid, or fumaric acid and sodium benzoate, or fumaric acid and boric acid, which composition or sub-combination compositions function as an antiseptic in retarding the bacterial decomposition of foods, as herein'set forth, and which composition, or its sub-combinations, is harmless to humans in the concentrations employed. These compositions may be applied to food as above illustrated in the raw state as a solution, or it may be applied as a solution and then frozen in situon the food, whereby later it may operate to tide over a period of failure of temperature maintenance; or the solutions may be frozen as ice and the ice applied tothe food and be available for actionas the ice melts. In the caseof juices, the chemicals of the invention may be applied directly to the juices. Thus the composition of my invention is characterized by its adaptability in that it may be applied in modes of application differing greatly in character and which are employed in the preserving of food. When applied in ice, it is preferable, in the case of many foods, to have the ice in crushed state.

Foods are being retailed in the frozen form more and more. The packer may use the utmost care in the selectin .of fine grades of food for packaging and freezing it under the utmost sani- 3 tary conditions and then, in spite of all this, the refrigeration may fail for one reason or another and the frozen package inadvertently partly thaw while the package is going through the various steps in reaching the consumer. After food has once been frozen and refrigeration is removed, it is well-known that it is perculiarly subject to dew terioration or spoiling. It is a fundamental purpose of my invention to provide an antiseptic preparation which will permit such food to be kept from spoiling due to temporary inadvertent thawing. Also, it is a primary purpose of my invention to preserve food which is not subjected to freezin temperatures. Also, it is such purpose of my invention to preserve fruits against the action of molds, and fungus growth.

In the shipping of lettuce, a layer of paper is placed in the bottom of the crate and then a scoop of crushed ice is put in the'bottom; then av layer of lettuce with the butts (the part where the roots are cut off) upwardly disposed; then a scoop of crushed ice is put over this layer of lettuce; then another layer of lettuce is put in; then another scoop of crushed ice is placed over these; then a third layer isput in and then a scoopof crushed ice is put over these butts; then paper is placed covering the top; and then the lid of the crate is applied.

After the crate is packed in the refrigerating car, crushed ice is also applied over the top of the crate. The ordinary temperature in a refrigeration car is about 33? F. If the temperature of the car was made colder there would be danger of freezing the product itself. Immediately upon shipping, the ice begins to melt about the product, and at the end of the five-day period, slime begins to form on the lettuce. Accordingly, if the shipment is going to involve a longer period, then often a re-icing is performed. It is the primary object and purpose of my invention to prolong this period and prevent slime forming. When slime forms, decomposition is taking place and that portion of the product so affected must be thrown away, and by so much, the total weight of the shipment is lost.

As another illustration, the preserving of fish caught atsea and taken aboard the fishing boat will next be considered. The particular species of fish to be considered will be thehalibut, which are difficult to preserve as Grade 1. Halibut are generally caught on hook and line, and after a catch has been made, which might be thirty thousand pounds, and the viscera removed, then the same is iced with crushed ice, Crushed .ice is placed in the poke (that is, in th belly of the fish from which the viscera has been removed) and then over the fish. Thereupon the ship proceeds, weather permitting, to make the next days catch, and these are treated the same as the first days catch. When the hold of the ship is filled with fish, the ship proceeds to port of sale. After a catch has been made on the fishing ground and before the hold is filled, it may be held by a storm,'and thus it may be delayed in returning to the port where it will unload to sell the fish for a considerable period of'time, such as two or three weeks. Halibut is a species of fish which is peculiarly subject to turning yellow on the outside and inside of the poke. When this happens, the fish can no longer be graded as No.

l and must take a lower grade and a correspondingly lower price. invention is to prevent the development of such yellow spots on the fish and the corresponding loss due to the degrading resultingtherefrom.

A primary object of my of foods.

set forth above, or the fish, for example as set forth above, it was a failure when used in concentrations which would not affect the taste or be present in too great amounts. Similarly, the antiseptic properties of sodium benzoate were likewise of such weakness that it was unable topreserve the said products, lettuce and fish, of said experiments for necessary periods of time. And the same is true of the maleic acid when applied alone in said experiments. However, when the three chemicals were applied in combination as set forth herein in connection with said experiments, they had the unexpected and the outstanding beneficial results set forth.

The combination of maleic acid and boric acid also gave unexpected results in increased antibacterial potency, as did also the combination of maleic acid and sodium benzoate.

After extended experimentation, I have discovered a composition of chemicals which is peculiarly effective as an antiseptic for foods and which is soluble in water and operatesto prevent and retard bacterialand fungus decomposition As solutions of said chemicals having said characteristics, I havediscovered that maleic acid has the property of increasing the potencyof sodium benzoate when formed in a solution; also that it has the property of increasing the potency of boric acid when in solution. These solutions, when in proper proportions as hereinafter set forth operate to extend the preservation of the food to which they are applied. The conditions for optimum results or less results are set forth herein. For optimum results the composition-of chemicals for achieving the purposes herein set forthwhich I have discovered, comp-rises employing all threeof said chemicals in the preferred range as follows: maleic acid 6 to 9 parts, boric acid 1 to 4 parts, andsodium benzoate 4 to 8 parts, in 32,000 parts of water or juices of fruits or vegetables.- The preferred formula is 7.5 parts maleic acid, 6 parts sodium benzoate, 2.5 parts boric acid, and 32,000 parts of water or juices of fruits or vegetables; The widest range is as follows: maleic acid 3.5 to 9 parts, boric acid 1 to 4 parts and sodium benzoate 4 to 8 parts, in 32,000 parts of water or juices of fruits or vegetables. 7

In the case of 'fumaric acid, We find the proportions of the preferred range is 7.5tov9 parts of fumaric acid and 4 to 8 parts of sodium benzoate and 1 to 4 parts boric acid. The widest range is as follows: fumaric acid 3.5 to 9 parts, boric acid 1 to 4 parts and sodium benzoate 4 to 8 parts in 32,000 parts of water or juices of fruits or vegetables; The preferred formula is 8 parts of fumaric acid and 8 parts of sodium benzoate and 32,000 parts ofwater or juices of fruits or vegetables. These chemicals; that is, fumaric acid or maleic acid and sodium benzoate and boric acid, when combined in accordance with my invention have their effective preserving power increase greatly over that when used separately. I have discovered that the fumaric acid or maleic acid, each of which have weak antiseptic properties when used individually, has an apparent synergistic effect upon the others-that is, the antiseptic properties of the boric acid and the sodium benzoate are so reacted upon in the solution that their preserving power is increased so greatly that they have a most important commercial value as food conforth in the'tables-of the experiments. The various members of my composition are :all soluble in water; therefore, 'they'can'beadded to water to make a solution and the solution as a whole frozen into ice; and the ice .is ordinarily applied in crushed form to the food. l Thus the composition of my invention is adapted to be applied .to the food .in the raw condition in :the standard manner of such application for :most of "the products to .be treated thereby. It will 'be understood that my composition when put'in a frozen :f-orm is only effective as the ice melts, or the chemicals :may be added directly to vthe-said.:yiu'ices forming the liquid component of the. combination, or thesol-ution'may be added-to the products treated as in the case of crabs, or the products may be dipped asi-n the case of vegetables or fruits, or the combinations of the dipping and the solution incrushed ice form may be empl Ed. Qne-of the features of the invention which-is particularly noticeable when added to juices is that it preserves the natural flavor of such juices; .in fact, the flavor of the products in all cases is substantially unaltered by the use .ofmy inven- U tion.

. My invention a-nd/ or discovery has established that the action of the fumaric acid: shows in general, and more or less closely, the results of its isomer maleic acid .in combination "with. the other chemicals set forth hereinin operating a bacteriostatic or fungicidal agent.

The following will readily disclose the toffee tiveness ofniy discovery or invention when-employing 'maleic acid in combination withthe other chemicals as herein set forth in the preserving of food in the .raw state. Firshtherecord .of preserving lettuce in crates will beset tort-h:

.Six crates of lettuce were packed; three of these crates were packed with ordinary ice as set forth hereina-bove, and three crates were packed after the .manner set forth hereina'bove but with ice prepared with my chemical solution. The six crates were placed in a room :of the same temperature as that provided for refrigerating car shipment, namely 33 that is, they were placed in a cold storage room having such temperature. Let it be noted that thetemperature must be such as .not to freeze the food product. After twelve days, one crate of each was opened; that is, one packed with the ordinary ice and one packed with the ice having the composition of chemicals of my invention, hereinafterreferred to as antiseptic ice. In the crate packedwith the ordinary ice the lettuce had become slimy and limp and decomposition commenced in every head without exception; only a small selected part of each head was at all usable for human consumption. In outstanding contrast, the crate packed with the antiseptic ice was free from slime. and-every head without exception was crisp. The heads were cut in half .so that the center was revealed, and in every instance they were crisp and fresh as when originally packed. There wasnosign of decomposition in any of the heads. a

On the 22nd day after packing, another crate of each wasopened-that is, a crate packed with the-ordinary :ice and a crate packed with. the antiseptic ice; the crate packed with the ordinary ice was wholly unfit for .human consumption. The heads were so slimy that there only remained a very small part in the center that might be used for human consumption. In short, the heads had reached that degree of .decomposition that in ordinary practice they are thrown" away. On the other hand, the "crate packed with the antiseptic ice of my invention and opened on the twenty-second day was found to beinithe same condition as the antiseptic ice- 'packed'crate opened on the twelfth day. There were'no signs of decomposition and no loss of weight was involved in doing any trimming because as stated there were no signs of any de composition. The lettuce was as crisp as when packed.

On :the thirtieth day after the packing 'ofsaid lettuce, the ice-:had all melted and a crate of each was again opened. The crate packediwith the ordinary ice was so badly decomposed that there was now nothing left that could (be .recovered. In the case with the crate packed with the antiseptic ice of my invention, some of the outer leaves of the heads needed trimming, but this was in no greater degree than "is ordinarily done when opened -:af-ter five days after packing with ordinary ice. vIn other words, the crate packed and opened 'on'the thirtieth day, contain- .ing the antiseptic ice, was found to be in .entirely satisfactory and in fine, keptand preserved condition. Each "and every head Was edible and in fact, was eaten. The crate was distributed to a number of persons, and the same taken home, eaten, and enjoyed as delicious by "all. Let it be noted that in packing cars of lettuce, the ice is also spread over the top of the crate as hereinabove set forth after the crates are placed side by side; but in the test above set forth, no 'ice was covered over the crate. In other words, the experiment was conducted :as a test under the most severe conditions. To experts in the shipping of 7 lettuce, the results were so surprising thatthey .ment was made in connection with fish. The

' record of such experiment will next be set forth.

.fish with ordinary ice.

A halibut fish ship was supplied with five tons of antiseptic ice of my invention. The ship proceeded to the fishing ground at sea and made its first catch of about twelve thousand pounds of halibut. After removing the viscera, this catch wasiced down with the five tons of antiseptic ice as herelnabove mentioned. A storm occurred so that it was six days later before the next catch was made. The ship proceeded to fill its hold and ice down the balance of enviscerated The fish were soldthat 'is, both lots; the first catch and the second catch-eon the eighteenth day. The oldest of the -fish packed in ordinary ice were graded No. 2.

These had been out of the water about twelve days and were found to have yellow spots both :on the inside of the poke and on the outside of the fish. While these were sold Ti-To. 2 grade, on the-other hand, in decided contrast, those packed with the antiseptic ice which had been taken from the water eighteen days previously were all free from any yellow spots whatsoever both on the inside of the poke and on the outside of the fish and were sold as Grade No. 1 fish. The total catch was about 30,000 pounds.

Thus, it is manifest that my invention is useful in preserving one of our great natural resources and will enable the fisherman to obtain the prices for Grade 1 and will also preserve the fish against loss due to decomposition, even when delayed by storms in returning to port. In this one field alone, the conservation advantages of my invention are of the utmost importance and were such that experts in that field did not believe it was possible to secure such outstanding results.

The solution employed in preparing the ice for both of the above experiments, that is, the experiment with the lettuce and the experiment for the fish, comprise by preferred formula, which is as follows: maleic acid 7.5 parts; boric "acid, 2.5 "parts and sodium benzoate, 6.0 parts,

in 32,000 parts of water. That .05 of 1% of chemicals could have such effectiveness is indeed most remarkable.

In providing a composition which is to serve as a preservative of food to be marketed, there is the limitation that it must not be required'in such large amounts in providing a useful preserving effect that it substantially affects the taste of the foods to be preserved. Moreover, such composition must be economical so that it is practical to be used in'preserving food. Thus, it is possible for foods which are produced in one part of the country to be safely and economically shipped to distant parts of the country, even entirely across the country, and by sea to distantports. Thus, the food treated by my invention may be shipped to ports where it is not now possible to ship it and it becomes available at such points without the loss and without the great danger of its being spoiled, due to unavoidable delays.

.In order to show in more detail what pro-por- 'tions are necessary to secure improvement in the preserving properties of the chemicals constituting my discovery and invention, namely, maleic acid or fumaric acid and sodium benzoate and boric acid, and just when the maleic acid or f'umaric acid operates to boost the preserving effects of sodium benzoate when used together in my invention, and when it, maleic acid or fumaric acid, begins to boost the preserving effect of boric acid when used together in my invention, and when it, maleic acid or fumaric acid, begins 'to boost the preserving effect of sodium benzoate and boric acid in combination, detailed tests and experiments are set forth in the tables given below.

These tables of tests and experiments are also set forth for the purpose of making clear the advantages of my invention even when optimum results are not required or desired, that is, when a shorter preserving period is sufficient.

In all the tests the controls comprised ordinary ice made from tap Water and the packing was done in the manner ordinarily and customarily followed in shipping and preserving the product to which the table relates. The water employed in preparing the solutions constituting my invention and discovery was tap water, that is, the same source was employed as used in connection with the controls. The tests set forth in the tables, it will be understood, are only a part of the many tests that were made and primarily only the tests leading up to, or related to, the critical point where changes begin to appear, are set forth. The results are illustrative of those obtained on the other products. In fact, my inventionhas proven successful on all food tested. What period of preserving is sufiicient, may be altered by difierent modes of transportation, so that a change in proportions which will provide another day or more of time in which the food may be held over untreated food may be a practical improvement. The tables also show the proportions for optimum results. Relative the proportions of the formulae: Of course, if one-half (16,000 parts) of water was used, with the same number of parts of the chemicals given for 32,000 parts of water this would be the same as doubling the amount of the chemicals. Wherever herein parts are mentioned, it is to be understood that the same refers to parts by weight.

The tables illustrating the effectiveness of maleic acid, an isomer of fumaric acid, are set forth to show the effect of the maleic acid upon sodium benzoate and boric acid.

Table I sets forth tests made on lettuce using maleic acid alone. This was done to give an illustration of the effectiveness of maleic acid when used in different percentages in preserving the lettuce. It will be noted that there was no Table I.Lettuce--maleic acid Grams of chemical used per400 lbs. End of End of End of End of End of of tap waterfrozen mto ice fidays Qdays 12days 18 days 30 days Controls, ordinary ice made from tap 15% 40% 80% Decom- Decomwater same as used with chemicals slime slime slime posed posed Total Sodi- Maleic um Boric grams Exp. acid, benacid, 2;

grams zoate, grams 1 grams ice Percent 16 40%. 80 Decomposed. Decomposed. 17 15% 40%... 80 do Do. 18 14%--- 36% 80 Do. 19 10%-" 28%-- 75 Do. 20 6%..-- 20% 70 Do. Good. l5% 60 Do. do 10%.. Do. 40 do 6%", 40 Do. do- 4%-- 40 Do. do. Good. 36 do Do. do. do.. 34 80%slime... Do. 7 do.. do." 25 60% slime... Do.

change until 18 grams of maleic acid were employed, when a substantial change was eiTected, and it was not until some twenty-gramswere used that a more nearly practicable result was provided. What constitutes a practical result would, of course, depend upon just how long it is desired to preserve the product.

Table II also sets forth tests made on lettuce using sodium benzoate alone. This was. done to ive an illustration of the effectiveness of sodium benzoate when used in different percentages in preserving the lettuce.

It will be noted than an improvement in the sixth day keeping power did not develop until there was about 88 grams of the benzoate employed, and for real effectiveness it required as much as 180 grams to provide a prolonged preserving period for the lettuce. When 182 grams were used, it appears that there was no; change.

10 benzoate, in some of the tests maleic acid and boric acid, and in some of the tests all three chemicals.

The tests show that when grams of maleic acid and 34 grams of sodium benzoate were employed, the results were good at the end of six days (that is, no slime), and at the end of nine days the slime had dropped from the control of 40% to 12% slime. Hence, this indicates that a positive boosting of the sodium benzoate takes place when 20 grams'of maleic acid are employed and 34 grams of sodium benzoate. From Table II it will be seen that when as much as 80 grams of sodium benzoate alone was employed, there was no advantage over the controls, that is, over ordinary ice packing.

Likewise, it will be seen that when 20 grams of maleic acid was employed with 14 grams of boric acid, there was an improvement over the con- Table II.---Le:.tuc e-sodium henzoate Grams of chemical used per 400 lbs. End of End of Endof End oi End of of tap water frozen into ice 6 days Q-days lZdays 18 days days.

Controls, ordinary ice made from tap 15% 40% 80%- Decoln- Decomwater same as used with chemicals slime slime slime posed posed Tote Sodi- Maleic um Boric 5.225;? Exp. acid, benacid, gfivem grams zoate, grams 4001135 grams ice Percent Percent 15%... 40 Decomposed Decomposed. 80 15% 40 80 do Do. 88 14%". 40 80 Do. 90 l0% 35 70 Do. 1. 32- 68- Do. 22- 50 D0. 180 Good 15' 40 Do 182 -.(lo 15' 40- Do.

l Beyond tolerance.

TableIII sets forth testsmad'e ,on lettuce usin trols in that at the end of .six. days there wasv only boric acid alone.

7 4% slime insteadof the control 15%, and. at the Table III .--Lettuceboric' acid I Grams of chemical used per 400lbs'. End of End of End of End of End of oi tap'waterfrozen into ice- 6 days :9 days. 1'2 days 18 days 30 days Controls, ordinary ice made from tap" 1 5% j 49% v 89% Decom- Decomwater same as used with chemicals shine shine slime posed posed Total Sodi- Maleic um Boric 5222:; Exp. acid, benacid, g in grams zoate, grams 4001138;

grams Percent Percent Percent 60 60 15 40 80 Decomposed Decomposed. 80 80 15 40 d D0; 90 90 12 40 D0. 100 100 11 35 D0. 150 9 30 D0. 180 5 20 D0.

From the table it appears that it required about" 1 end of nine days there was a drop from the con- 90 grams of boric acid to provide a change of trol 40% slime to 15% slime, etc., Thus, i-tis 3% on the sixth day keepingpower and that it I was not until 180 grams were employed thatthe;

slime was reduced after six days to. 5%, after .70

nine days to 20%, and after twelve days to 50%, and that it did not keep at allfor eighteendays. at which time it was decomposed and had. to be discarded.- Table IV sets forth tests made on lettuce usin s'hown'that when 20 grams of maleic acid are.em-' played with 14 grams of boric acid, there is a boosting of the potency of the boric. acid. Refme ring to Table III, it will be seen that no eflect of theboricacid over thecontrol at the end of si pdayswa's developed "until 90 grams of'boric acidewas employed. Also it willbe seen that the 'mal-eic' acid employed in the proportion of 20 in some of the tests maleic' acid and sodium 75 grams had a boosting efiect' to the combination Grams of chemical used per 400 lbs. End of End of End of End of End 01 of tap water frozen in to ice 6 days 9 days 12 days 18 days 30 days C ontrpls ordinary ice made from tap 15% 40% 80% Decom- Decomwater same as used with chemicals slime slime slime posed posed Total Sod1- 7 Maleic um Boric i Exp. acid, benacid. g in grams zoate, grams 400 lbs grams 20 34 54 Good.. 12%... 35%--. 80% slime... Deoomposed. 20 14 34 4% 15%... 4O Decomposed. Do.

34 14 40% slime..- 20 44 24 .dO 25 34 25 14 25 34 14 25 41 24 34 30 14 30 34 14 30 30 30 35 34 35 14 35 35 2O 35 34 14 34 40 14 15% 40 34 16 Good..

40 34 14 88 .--(10-.. D0. 42 34 76 .do... 0 18% slime. 42 14 56 .do... 17% S11 20% slime. 42 '14 34 90 ...do... 12% slime.-. 15% slime. 42 48 00 ...do... Good 10% slime.

42 48 90 --.do... 5% slime-.. 18% slime. 42 34 14 9O Excel- Excellent- 3% slime.

42. 7 34 14. 2 90. 9 D0. 44 34 14 92 D0. 44 34 14 92 Do. 48 34 14 96 D0. 48 34 14 96 D0. 52 34 14 100 D0. 52 34 14 100 D0.

It will be seen that it required 18 grams of maleic acid when used alone to show any advanv tage at the end of nine days. No advantage was shown at the end of twelve days. Likewise, in the tests it will appear that when. 19 and 20 grams of maleic acid were employed, the results showed an improvement of 5% in the preserv ing of the fish at the end of 12 days.

Wit-h sodium benzoate, the tests show that it Table V.--Salmon(silver) Grams of chemical used per 400 lbs. of tap End of End of End of End of End of water frozen into ice 6 days 9 days 12 days 16 days 21 days g gggggg fi i g ggg water Good preserved 40% preserved Putrid Putrid Total Maleic dium Boric 52:3? Exp. acid, benacid, ative in grams zoate, grams 4001bs grams ice 15 Good 60% preserved.-. 40%preserved..-

18 ...do. preserved--- .----do 19 -..do..- preserved.-. 30 .--do... preserved.-. 40 ...do... preserved.-. 60 .-.do... do -....do 15 ...do... 60% preserved... 40% preserved... -.-do... .-...do o ,150 ---do. 65% preserved... 45% preserved.

15 ...do... o 200 o... 65% preserved..-

13 required 1 50- grams before improvement w-as made at the end of nine days, and likewise at-the endof twelve days.

With boric acid-itrequired 200 gramsbefore improvement resulted at the end of nine days, and there wasno improvementat the end of twelve days over the control.

In treating cauliflower, the cauliflower is dipped in the-solutin-of iny invention, preferably'in' my solution of maleic acid, 6 to-9 parts, sodium benzoate 4 to 8 parts, and boric acid l to-i parts; or my preferred formula of maleic acid 7.5" parts, sodium benzoate 6 parts ,--and---boric acid 2.5- parts in- 32,000 parts of water, for-a period of time sufficient to penetrate all through said product. This may extend 'tento twenty minutes. These may or-may not be wrapped in paper'or' cellophane and then shippedto the market; These kept for three weeks in excellent marketable condition, whereas when packed according to normal procedure the product keptinot to exceed six days Without turning yellow It will'be remembered-that such yellow portion is normally required to be-trimmed off and thereby there is a loss by-so much of the product. However, the-very serious objectionis due-to the fact that there is a loss in-sale value. The articleby such yellowing immediately shows thatit is not fresh.

In treating celery with my invention, it-iss'ub jected to a solution ofone of my said formulae by dipping or by spraying. The celery is then put crates andthen held in cold storage. When-shipped it-i's held in refrigerated cars as in normal shipping conditions of the present time.

Kale may likewise be dipped or'sprayed with one of the said formulae of my invention.

Carrots may be dipped or sprayed with a solution of one of my said formulae and thenare held in cold storage. When shipped-for short distances, they maybe iced with ice formed from a solution of one of my formulae withoutbeing placed-in refrigerator'cars. If long distances are involved,- then they would be placed in refrigera'tor cars, with or without ice, preferably with ice formedfrom the-solutionof oneof my formulae- I I Table VI'sets forth tests made onfish (silver salmon-)- when maleic acid, sodium benzoateancl boric acid were all three employed in combination and in different percentages.

'I't'will be noted that it required 32.68 grams of maleic acid, 36.85grameof sodium benz'oate, and 21.3? grams'e'f boric acid to provide an increase at-the endof seven days of in the preserving powerofthe composition over the control, and at the end or l4 days there was a 20% increase in the preservingpower. The fraction of grams is set 'forth-to give a sumtotal of 90.9 grams for use-in a 400 pound block of ice. When this is multiplied by five',-it gives slightly'over 16 ounces. The preferred formula has the proportions of 42.8 grams of malei'c "acid, 34.0 grams of sodium benzoate, and'14.10 grams of boric acid. This showed a 99% preservation of the fish at'the end of seven days, a 97% preservation at'the end of 14 days, and a 95%jpreservation at the end of 21 days. The bloom of the fish was preserved and in every respect a superior product resulted.

Thetestsalsosh'ow that increasing the amount of the total chemicals present beyond that of the preferred formula did "not give results as. favorable as those when the preferred formula was used, but did provide avpractical composition.

Table VI .-'Fish-"-( silver salmon) Prcscrvationin pcrcentagcs'v Ounces .0! chemicals used for 2,000

lbs. tap

water made 'in-.. to ice Ordinary tap water ice Gondition of fish end of 21 days Coildition of fish end of 14 days Gondition of fish end of 7 days Controls, ordinary ice made from tap water same as used with chemicals;

Putrid 50 --diS- Combined preservative ices, grams chemical used in 400-lb. blocks'oi ice.

36. sodim benzoatc -21. 37 boric acid Exp. 1 50 [32.08 mast acid 90.90.; ,34. 2O maleic acid 36. 8-5 sodiumbenzoate; 19.85 Boric acid.

0.90.2.0; {35x50 maleic acid Exp.2.. 95

i i i 35.50 Sodium benzoate 10.90 boric acid;

Exp. 3..

90. 9o 40/00 male'icacid. 34.00 sodium ben' 16.90 boricaoid Exp. 4.- .95

V Li 42.80 maleicacid 34.00 sodium benzoate;.. Exp.5 14:10 boricacid 9O..'i() 45.36 maleic acid 34.20 sodium benzoate 14.17 boric acid Exp. 6..- 99

93.73 l 51.03 maleicacid 34:20 sodiumbenzoate 14.17 boricacid Aseriesof cookingv testswas conducted on fresh ocean crabs, known as Deep Sea orDungeness crabs, with the'preservative of my invention, for the purposeof ascertaining its. preserving quality. onfcr'ab.

Thesecr'abs were all alive when placed in the vats, and before dropping them-in the'boiling water the fishermen tore their backs oiiy'as -is the 'usual'custom for:better.keepi-ng,:.b'ecause then the entrails alsoare removed, thus leaving only bone and :fiesh. The: crabs.-for control purposes, were cookedv in boiling wateri itap') intheordinary or custom'ary'manner" for 15 minutes, :and some were c'ooked for15 minutes in boiling water to which. .had been added my preservativechem.-v ical's, the proportions being 3.2 ounces" per 50 gallons (400 lbs.) of water,- i. e.,'in 'th'e proportion'of l6 ounces.to2,0'00 lbs. The 3.2 ounces of chemicals consisted of. maleic acid 7.5 parts, 'so dium .benzoate '6 .partsyand boric:acid 2;5 .parts by weight; After cooking:- and. cooling the meat was cracked from the' bones and -.'placed inig'lass' jars with caps screwed on, but :nothermetically sealed. Then the jars were placedina'refrigerator, i. e., held in cold storage, and held atwap-x proximately 33 F., all :inthe customary man ner. At. each inspectiomtwo jars ofeach were opened, that is, the leg meat and body were each packed in separate jars, therefore two jars opened. Crab imeat. packed in this manner, leg and :body meat separate, keeps longer than when packed whole, the limit being from eight to t'en days. The resultswere:

Gounod-Opened Y on :the 10th dayih'ad strong carded 15 odor and pronouncedinedible. Unfrozen crab meat is not expected to last beyond eight days maintained at about 33 F. This is why the product treated with my invention was opened on the tenth day, as it would not expected that the ordinarily packed or control product would keep that long. Any advantage by reason of the invention or discovery should appear then or thereafter.

Treated crab meat-On the 10th day both body and leg meat in excellent condition; fine flavor and taste. On the 17th day excellent, with good flavor and taste. On the 24th day, still in excellent condition and edible. On the 31st day, still in good condition and edible. On the 38th day the body meat had a slight ofi-odor and taste, while the leg meat was still in good condition and edible.

My invention or discovery was also tried on pure and fresh apple juice. The preferred formula of my invention was employed in the proportions of maleic acid, 7.5 parts by weight; boric acid, 2.5 parts; and sodium benzoate, 6.0 'parts in 2,000 pounds of juice. The chemicals of my composition were added in the powdered form directly to the juice. The product was tested. at the end of 3 days, 7 days, 14 days, 21 days, 28 days and 36 days. The treated product, at the end of said periods respectively, showed no mold and the production of no thick matter called mother. The control product clearly showed "mother? and mold as early as the fourth day. So far as the treated product was concerned, no change in the sweetness could be detected. The experiments and tests were all conducted at room temperature, 65 F., in the presence of experts.

Tests were also made on orange and grapefruit juice. These were not hermetically sealed, the caps being only screwed on the jars. They were treated with the preferred formula by being added directly to the juice. The control showed mold at the end of the eighth day, while there was no mold on the treated product. This held true for the treated product on the 16th day and its flavor unchanged. The juice was unheated. The tests were conducted at room temperature, that is, 65 F'., in the presence of experts.

,My invention or discovery was also tried on the retardation of bacterial and spore producing mold on the skins oforanges, lemons, grapefruit,

tangerines and guava fruit. After the said fruit was subjected to washing in the customary procedure, said fruit was treated with a solution of my preferred formula (maleic acid 7.5 parts by weight, sodium benzoate 6.0 parts, and boric acid 2.5 parts in 32,000 parts of water) for a period of 3 to minutes, by immersing while traveling through the vat, the temperature being from 100 F. to 115 F. A colder solution would take longer. These were exposed to the air and dried, and then wrapped in thin paper, all in the usual manner. There was noticeable residue on the skin of the treated fruit. Said experiments proved successful.

As a specific example, oranges will be considered. On the control, the crates packed-in the usual manner and untreated, showed from 15% to 25% mold in 30 days. In contrast, oranges of same grade, simultaneously packed and treated with my invention as set forth above, showed no mold at all at the end of 30 days. Likewise at 60 days, the oranges treated with my invention showed no mold. At 90 days said treated oranges in an entire crate (about 80 Sunkist oranges) showed one orange with a mold spot of the size of a quarter coin. At 120 days, saidtreated oranges in an entire crate (about Sunkist oranges) showed two oranges with mold spots of the size of a quarter coin.

An interesting test was made on some untreated oranges on which heavy, powdery blue mold had formed on'one-half of each orange. These oranges were dipped into the solution of my invention of preferred formula as set forth above, for a period of 15 minutes, after which the said fruit was placed on a shelf' in the laboratory in open air for observation at room temperature. The mold dried up and did not spread further. whole orange dried up with no more mold appearing. Normally when the mold starts, the entire orange will rot through.

One of the great advantages of my invention or discovery is that it preserves foods with their natural taste or flavor for a plurality of times longer than is heretofore thought possible. Foods treated with .my invention or discovery need not be frozen and therefore may have their natural taste, whereas it is well-known that serious objection has obtained to many types of frozen food in that the original flavor is lost.

Particularly is this true of fish. It is to be noted that products which are preserved by quick freezing have the disadvantage that they must be used immediately when thawed out, so that it is a distinct advantage when the food can be preserved without quick freezing, both as to its taste and as to when it may be used. The natural appearance of the products is preserved by my discovery and invention. In the case of fish, it retains its bloom and freshness in appearance. In the case of vegetables, their freshness is retained.

In applying the composition of my invention, the same may be continuously sprayed as a solution so that after it is sprayed upon the upper part of the product it may drip down through the product, be collected and resprayed from above and thus be kept in circulation and thereby keep the product from decomposing by bacteria while in the raw state. This has particular application to the food on counters and in cases in stores. The present preferred from of application is to have the solution of my invention frozen into ice, then crushed, and then applied to the food, and/or it may be put over the open lettuce containers having the food therein, so that the melting ice may drip through the container. An-

other method of applying the antiseptic composition of my invention is as follows: In cold storage houses where fish are preserved, the fish are dipped in water and then removed, so that the film of water may be frozen in place on the fish, and this is repeated until a coating of ice of considerable thickness is provided on the fish. Then these fish are hung up and kept for as much as a year in cold storage under freezing temperatures and not allowed to thaw out. The danger arises when they are removed and are passing through the retailing steps for consump tion, it being well-known that food once frozen is peculiarly subject to spoiling rapidly upon thawing. The dipping water may be prepared with my invention, that is, having my composition of chemicals above set forth dissolved therein, and the film of ice prepared just as above described and then dipped again and another film applied until a coating of ice of the desired thickness is provided for the fish. Then, when the fish is removed at the end of whatever period it is desired to remove them, the'melting ice operates to pre- After two or three months the 17 serve the fish, and they will not be subject to as prompt decomposition or deterioration as at present.

In the case of frozen foods, the composition of my invention may be applied as follows: The food can be dipped in the solution before freezing or the solution can be sprayed upon the food, such as peas, and then the package frozen; thus, if inadvertently the package should become unfrozen before use, the composition of my invention would operate to preserve the food from spoiling until the same is refrozen.

The various methods of applying my invention set forth above will serve to illustrate the great variety of modes in applying the same, and its wide range of utility.

My experimentation with fumaric acid paralleled the results of the maleic acid so far as increasing the eifectiveness of sodium benzoate and boric acid is concerned. This is made clear by the following table:

Table VII [Two silver salmon fish were used in each of these tests, and iced in the usual commercial way. The bacteriologist calculated the preservation in percentages rather than by the usual per-million count. The table below gives the amount of chemicals put in the 400 lbs. of water and frozen into ice] re e vet s in percentages .(f)u]r]1ces o c em- Oldmary i gffi was used icals for oondioondi- Condic o 1 ton of tion 7 tion tion ice of fish of fish of fish end of end of end of 7 days 14 days 21 days Controls, ordinary ice made from 80 50 Unfit tap water same as used with for chemicals. use- Discarded Grams chemicals used [or 400 lbs. ofwater 42. 80 fumaric acid 7. 34.00 sodium benzoate 6.0 Exp.1 14.10 boric acid 2.5 85 70 50 51. 03 fumaric acid 9. 0 34.20 sodium benzoate 6.0 Exp. 2.. 14.17 boric acid 2. 5 90 80 60 42.80 maleic acid 7. 5 34. 00 sodium benzoate. 6. 0 Exp.3 14.10 boric acid 2.5 99 97 95 51.03 maleic acid 9.0 34. sodium benzoate 6.0 Exp.4. 14.17 boric acid 2.5 97 90 80 It will be noted that at the end of 7 days with untreated ice used for control and prepared from v the same character of water, namely, tapwater,

that was used for the chemicals, there was an I Experiment No. 1 using the quantities of chemicals, fumaric acid, sodium benzoate and boric acid, there set forth, at the end .IOf '7 days 385% of the fish was preserved, that is, lack'dfdeterioration of any degree; at the end of 14 days there was preserved; and at the end of 21 days there was 50% preserved. In experiment No. 2 with the quantities of chemicals there set forth there was a 90% preservation at the end of 7 days, that is, lacked deterioration of any degree; atthe end of 14 days there was an preservation; and at the end of 21 days there was a 69% preservation.

In order to show in more detail What proportions are necessary to secure improvement in the preserving properties of the chemicals constituting my discovery and invention, namely, fumaric acid, sodium benzoate and boric acid; fumaric acid and sodium benzoate; and fumaric acid and boric acid, further detailed tests and experiments are set forth in the tables below.

Table VIII sets forth the tests made on fish using fumaric acid and sodium benzoate, and likewise Table IX sets forth tests made on lettuce using fumaric acid and sodium benzoate Table X sets forth the tests made on English sole with solutions of various combinations of the chemicals of my invention. These are set forth as an illustration of how closely the action of fumaric acid parallels the action of maleic acid as set forth in the co-pending applications Serial Numbers 734,561, 202,569, and 232,008. Again, what cons'titutes a practical use, would, of course, depend upon just how long it is desired to preserve the product. It is academic that salmonella organisms (bacteria) are among the most resistant contaminates on dressed poultry, and, of these organisms salmonella typhosus is particularly most most difficult to kill. Using my invention I have found that fumaric acid present in the proportion or 8 parts and sodium benzoate present in "the proportion of 8 parts to water in the proportion of 16,000 parts kills said culture in the period of ten minutes exposure. A weaker solution retards the growth of the organisms. This shows how positively effective is my invention.

Tables VIII, IX-and X are as follows:

Table VII.

[Six silver salmon fish were used in this test and iced in the usual commercial way. The bacteriologist calculated the preservation in percentages rather than by the usual per million count. The table below gives the amount of chemicals put in the 400 lbs. of water and frozen into ice.1

Table IX relative lettuce shows that by con- "tinuing to increase the furnaric acid component very excellent results are obtained, that is, when the components were present in the proportion of 8 parts of fumaric acid and ,8 parts of sodium benzoateandBZJJflO parts of water. These results also, further confirm ,the parallelism of the action of fumaric acid with maleic acid.

wipes Table IX .-Lettuc*e Ounces of chemical used per 2,000 End of End of End of End of End of lbs. of tap water frozen into ice 6 days 9 days 12 days 18 days days Controls ordinary ice made from tap water same as used with 15% slime slime 80% slime chemicals pose pose 8. 0 fumarie acid No slime No slime No slime No s1ime 1% slime Exp 1 8. 0 sodium benzoate Excellent. Excellent- Excellent- Excellent- 8.0 furuarlc acid Exp. 2-.-. sodium do -.do do do 3% slime.

Table X.--Treatment of English sole (Puget Sound) with ice containing ,fumaric acid, sodium benzoate and/01' boric acid Preservation in percentages Ounces of Ordinary tap water ice was 32 2 Oondi- Condi- Oondiused for control 01,1 tion of tion of tion of Condition Condition Condition ton fish end fish end fish end of fish end of fish end of fish end Once of 6 of 12 of 15 of 18 days of 21 days oiMdays days days days Controls, ordinary ice-made 80 Dis- Discarded Discarded Discarded from tap water same as carded used with chemicals.

Grams chemicals used for 400 lbs. of water Exp. 1. 90.0fumaric acid- 16.0 90 50 10 Discarded. Discarded. Discarded.

67. 5 furnaric acid 7. 5 22.5sod.benz0ate. 2.6 90 80 50 90.0 10.0 61.8 fumaric acid 7 6.8 22. 5 sod. benzoate 2. 5 Exp. 3. 5.6boric acid 1.0 90 80 60 40 Do.

15.8 50.6 in eacid..- 8.8 33. 75 sod. benz0ate. 6.0 Exp. 5. 5.6 boracacid .1.0 95 95 90 85... l. 50.

15.8 8.0 Exp. 95 95 05 95 70 preferred.

16.0 8.0 6.0 Exp. 2.0 05 95 85 80 50.

16.0 6.0 8.0 Exp. 4.0 85 80 80 75 6C 50.

18.0 4.0 8.0 Exp. 4.0 85 80 80 75 60 50.

16.0 2.0 8.0 :;p. 6.0 80 75 6G 50 Discarded. Discarded.

16.0 8.0 Exp.l1 so so 40 Discarded. ....do Do.

8.0 E 2 95 95 85 1o 6C.

Relative Table X.-From the above it is seen that the formula. of 8 parts of fumaric acid and 8 parts of sodium benzoate gave very excellent results, namely, 95% at. the end of six days, 95%

even as late as eighteen days, and 85% at the end of twenty-one days, so that this constituted the preferred formula.

Table XI.*Clams.

[On February 2, 1951, a quantity of live clams.(speeies+ Butterand heel; clams-also known as little neck clams) were treated with the solutions of my invention.]

Test No.

Dipped 3 Butter clams while still alive and in the shell into a solution formed as follows: One part of the chemicals of my invention, for example, comprising 50- iumaric acid and 50-sodium benzoate were added toone thousand parts of sea water. This will be herein referred to as the one to one-thousand proportion solution of the invention. They were treated for 60 minutes, opened and then placed in sealed jars. The jars were then placed in a refrigerator. 7

Dipped 3 Butter clams while still alive and in the shell into a one to one-thousand-proportion solution in which ordinary tap water was used. They were treated for 60 minutes. The shells were openedand the clams were put into a sealed jar. The jar was then placed in a refrigera or.

Dipped 3 clams (little neck.) while still alive and in the shell into a one to one-thousand proportion solution in which sea water was used. They were treated for 60 minutes, opened and the clams were placed into a sealed ion The jar was then placed in a refrigerator.

Dipped 3 Rock'clams (little neck") while still alive and in the shell into a one to one-thousand'jproportion solution in which ordinary tap water was used. They were treated for 60 minutes. opened and the clams were put into a sealed jar. The jar was then placed in a refrigcrater.

Dipped 3 live Butter clams, taken out of the shell, into a one to one-thousand proportion solution in which sea water was used. They were treated for 3 minutes and then put into a sealed jar. Thejar was then placed in a refrigerator.

Dipped 3 live Butter clams, taken out oi the shell, into a one to one-thousand proportion solution in which ordinary tap water was used. They were treated for 3 minutes, out into a sealed jar and placed in a refrigerator.

Dipped 3 live Rock clams, taken out of the shell, into a one to one-thousand proportion solution in which sea water was used. They were treated for 3 minutes, placed in sealed glass jar and then put into a refrigerator.

. Dipped 3 live Rock clams, taken out of the shell, into a one to one-thousand proportion solution in which ordinary tap water was used. They were treated for 3 minutes, put into sealed jars and placed in a refrigerator.

In all cases above the refrigerator temperature was 'from 34 to 36F.

Results of above tests February 9, 1951:A1l jars weretaken from the refrigerator, opened andcar'efully examined. All "the clams had their natural bloom andfresh appearanceand all were free from any off-color odor.

February 12, 1951: All clams were in excellent condition and were free from anycfi-color odor.

February 1 9, 1951 All clams-were in excellent condition, having a freshappearance and were 'free from any off-odor.

' Fbruary 23, 1951: All clams were fre'e from any oil-odor andhad a fresh appearance.

February 27, 1951: All clams were'fr'ee from any-'ofi-odor and had a goodappearance excepting Tests #30 and #33. These two'had an off-odor and were losing their natural 'fiavor.

Controls for above clam tests "discarded.

Thus, it is seen that without the :"b'enefit of applicants invention the clams lasted someseven -days whereas those treated lasted twenty-five da5ys wi ththe exception of Tests "#30 and #33. 1 Apparently there was no difference whether sea water 'or 'tapwater was employed, and: it made little difierence whether the clams were dipped 22 into the solution of the invention while "still the shells and thereafter removed from'th'e shells and put in the jars, or whether they were removed from the shells and then treated with the solution of the invention and then put into the jars.

When the deterioration proceeds to the point that 25% of the fish is spoiled then the fish so far as food is concerned is no longer useful. In carrying out the experiment, the ic'ein the control was renewed daily as it melted and the same in the case of experiments Nos. '1 and 2 of Table VIIthe fish not being frozen. The object was to keep the fish covered with ice.

It will be understood that the tests were made in a room where the temperatures were above freezing, approximately 33 F. to 35 F. so that there was a melting of the ice which required replacement daily.

The various members of my composition are all soluble in water; therefore, they can be added to water 'to makea solution, and the solution as a whole frozen into ice; and theice isordinarily applied in crushed form to the food. Thus the composition of my invention is adapted to be applied to the food in the .raw conditioninthe standard manner of such application for most of the products tobe treated thereby. Of course, in the case of juices, the chemicals are applied directly to the juices and the ,juice forms the liquid part of thesolution. It will be-understood that my composition when put in a frozen form is only effective as the ice melts.

The above experiments establish'the similarity of action of fumaric acid with its isomer, maleic acid, when combined inan aqueous solution with sodium benzoate and/or boric acid.

It should be noted that sodium benzoate is preferred over benzoic acid, among other reasons because of its greater solubility.

Furthermore, these experiments establish the fact that when fumaric acid, like its isomer, maleic acid, is employed in forming a solution with sodium benzoate and boric acid,'or with'one or other of the last two agents, that greatly improved results in providing preserving properties and other advantages result in connection with the product which is treated. Whether this comes about by reason of synergistic action or whether it is a result of catalytic acti0n,1or Whether it is the result of reaction products formed by combining the said compounds in a solution, or whatever may be the cause, atsleast my teaching shows that an efiicient commercially practical and very economical composition "results. Whatever the full scientific explanation is it has not been determined up to the present time. The developmental work has established definitely that it is an efiective and economical bacteriostatic and fungicidal agent. -It finds an important field of application in connection with food. Since the disclosure of my discovery or invention provides a teaching which affords a very practical commercial advantage in*the preserving of food and a preventative of develop 400 Lbs.=l81,'440 grams= 6,400 ozs; 2,000 Lbs.=907,200 grams=32,000 ozs.

20 grams d 1s1,440=s.5 $2,000 minimum 30 grams g 1s1,4 0=5.3 =32,000 minimum 35 grams 181,440=6.17:32,000 preferred 40 grams 42 grams l8l,440=7.4 232,000 preferred 42.7 grams l8l,440=7.5 :32,000 preferred 44 grams best l8l,440=7.76:32,000 preferred 48 grams l8l,440=8.46:32,000 preferred 52 grams l81,440=9.l7 132,000 preferred 20 grams were taken as the minimum because the experiment showed with that amount a substantial and marked improvement over the controls (untreated product) resulted. This minimum amount showed a definite retarding action on the mold or bacteria organism as the case might be. In fact, the invention has proven effective in the retardation of said organisms which attack food products or products of an organic character which support said mold or fungus growth and bacteria.

Iclaim:

1. .A bacteriostatic fungicidal solution for retarding decomposition of food wherein fumaric acid, boric acid, and sodium benzoate, respectively, present in the proportions as between the components of 7.5 parts to 9 parts of fumaric acid, 6.0 parts of sodium benzoate, and 2.5 parts boric acid, and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

2. The method of retarding decomposition of food comprising treating food with a bacteriostatic and fungicidal solution formed of fumaric acid, boric acid and sodium benzoate dissolved in water in the proportions of 7.5 parts to 9 parts of fumaric acid, 6.0parts of sodium benzoate and 2.5 parts of boric acid and not more than 32,000 parts of water.

3. A bacteriostatic fungicidal solution for retarding decomposition of fish wherein fumaric acid, boric acid and sodium benzoate, respectively, present in the proportions as between the components of 7.5 parts to 9 parts of fumaric acid, 6.0 partssodium benzoate, and 2.5 parts boric acid-and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

4. The method of retarding decomposition of fish comprising treating fish with a bacteriostatic and fungicidal solution formed of fumaric acid, boric acid and sodium benzoate dissolved in water in the proportions of 7 .5 parts to 9 parts of fumaric acid, 6.0 parts of sodium benzoate, and 2.5 parts of boric acid and not more than 32,000 parts of water.

5. A bacteriostatic fungicidal solution for retarding decomposition of food in the form of ice prepared from a solution wherein fumaric acid, boric acid and sodium benzoate, respectively, present in the proportions as between the components of 7.5 parts to 9 parts of fumaric acid, 2.5 parts of boric acid, and 6.0v parts of sodium benzoate, and. not more than 32,000 parts of Water, contribute an effective portion of the preservative result. 7 V Y 6. The method of retarding decomposition of food comprising treating food with ice prepared from a bacteriostatic and fungicidal solution formed of fumaric acid, boric acid and sodium benzoate dissolved in water in the proportions .of 7.5 parts to 9 parts of fumaric acid, 2.5 parts of boric acid, and 6.0 parts of sodium benzoate and not more'than 32,000 parts of water.

7. A bacteriostatic fungicidal solution for retarding decomposition of fish in the form of ice prepared from a solution wherein fumaric acid, boric acid and sodium benzoate, respectively, present in the proportions as between the components of 7.5 parts-to 9 parts of fumaric acid, 2.5 parts of boric acid, and 6.0 parts of sodium benzoate, and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

8. The method of retarding decomposition of fish comprising treating fish with ice prepared from a bacteriostatic and fungicidal solution formed of fumaric acid, boric acid, and sodium benzoate dissolved in water in the proportions of 7.5 parts to 9 parts of fumaric acid, 2.5 parts of boric acid, and 6.0 parts of sodium benzoate and not more than 32,000 parts of water.

9. A bacteriostatic fungicidal solution for retarding deterioration and decomposition of food wherein an unsaturated dibasic acid with four carbon atoms, boric acid and sodium benzoate, respectively, present in the proportions as between the components of 7.5 parts to 9 parts of said unsaturated dibasic acid, 2.5 parts boric acid and 6.0 parts sodium benzoate, and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

10. The method of retarding deterioration and decomposition of food comprising treating food with a bacteriostatic and fungicidal solution formed of an unsaturated dibasic acid with four carbon atoms, boric acid and sodium benzoate, dissolved in water in the proportions of 7.5 parts to 9 parts of said dibasic acid, 2.5 parts of boric acid, and 6.0 parts of sodium benzoate and not more than 32,000 parts of water.

11. A bacteriostatic fungicidal solution for retarding deterioration and decomposition of food in the form of ice prepared from a solution wherein an unsaturated dibasic acid with four carbon atoms, sodium benzoate and boric acid, respectively, present in the proportions as between the components of 7.5 parts to 9 parts of said dibasic acid, 6.0 parts of sodium benzoate, and 2.5 parts of boric acid and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

12. The method of retarding deterioration and decomposition of food comprising treating food with ice prepared from a bacteriostatic and fungicidal solution formed of an unsaturated dibasic acid with four carbon atoms, sodium benzoate and boric acid, dissolved in water in the proportions respectively of 7.5 parts to 9 parts of said dibasic acid, 6.0 parts of sodium benzoate, and 2.5 parts of boric acid and not more than 32,000 parts of water.

13. A bacteriostatic fungicidal solution for retarding deterioration and decomposition of fish wherein an unsaturated dibasic acid with four carbon atoms, sodium benzoate and boric acid, respectively, present in the proportions as between components of 7.5 parts to 9 parts of said dibasic acid, 6.0 parts sodium benzoate, and 2.5 parts boric acid and not more than 32,000 parts of Water, contribute an effective portion of the preservative result.

14 As a bacteriostatic and fungicidal article of manufacture for retarding the deterioration and decomposition of food, the composition consisting of 7.5 parts to 9 parts of fumaric acid, 6.0 parts of sodium benzoate, and 2.5 parts of boric acid to bed ssolve not mo e n. 32.00 partsof. wat r.

' As a b cteri statie and; fung article of manuf cture f r retardi g he d t o n and decomposition, of food, the composition consisting, 02.7.51 parts to 9 parts of an unsaturated dibasic acid with four carbonatoms, 6.0 parts of, Sodium benzoate, and 2.5 parts of boric acid to be dissolved in not more than 32,000 parts of water.

16. A bacteriostatic, fungicidal solution for retarding decomposition of food wherein fumaric acid and sodium benzoate, respectively, present in the proportions as. between components of 3.5 parts to 9 parts, and 4 partsto 8 parts, and

not more than 32,000 parts or water, contribute an-efiective portionv of the preservative result.

1.7. A bacteriostatic fungicidal solution for retarding decomposition of food wherein fumaric acid and sodium benzoate, respectively, present in the proportions as, between components of 8 parts an 8 pa t and not. mo than 32.000 parts f w ntribute. an ffe t ve. p r ion of the preservative result.

18. The method of retarding decomposition of food comprising treating food with a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the proportion of 3.5 parts to. 9 parts of fumaric acid and 4 to 8 parts of sodium benzoate in not 1 more than. 32,000 parts of water.

19. The method of retarding decomposition of food comprising treating food with ice prepared from a bacteriostatic fungicidal solution formed of fumaric acid and'sodium benzoate dissolved in water in the proportion of 3.5 parts to 9 parts of fumaric acid and 4 parts to 8 parts of sodium benzoate in not more than 32,000 parts of water.

20. The method of retarding decomposition of food comprising treating food with a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the following proportions, 8 parts of fumaric acid and 8 parts of sodium benzoate in not more than 32,000 parts of water.

'21. The method of retarding decomposition of food comprising treating food with ice prepared from a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the following proportions, 8 parts of fumaric acid and 8 parts of sodium benzoate in not more than 32,000 parts of water.

22. The method of retarding decomposition of vegetables comprising treating vegetables with a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the proportions of 3.5 parts. tov 9 parts of fumaric acid and 4 parts to 8 parts of sodium benzoate in not more than 32,000 parts of water.

23. The method of retarding decomposition of vegetables comprising treating vegetables with ice prepared from a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the proportions of 3.5 parts to 9 parts of fumaric acid and 4 parts to 8 parts of sodium benzoate in not more than 32,000 parts of water.

24. The method of retarding decomposition of vegetables comprising treating vegetables with a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the following proportions, 8 parts of fumaric acid and 8 parts of sodium benzoate in not more than 32,000 parts of water.

h m t d of re ard g eco position of vegetables comprising treating vegetables with ice prepared from a bacteriostatic fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the following proportions, 8 parts of f umaric acid and 8 parts of sodium benzoate in not more than 32,000, parts of water.

26. A bacteriostatic and fungicidal solution for retarding organic decomposition wherein fumaric acid and sodium benzoate present, respec-. tively, in the proportions as between components of 3.5 parts to 9 parts. fumaric acid, and 4 parts to 8 parts sodium benzoate, and not more than 32,000 parts of water, contribute an effective portion of the preservative result,

27. A bacteriostatic and fungicidal solution for retarding organic decomposition wherein iumaric acid and'boric acid present, respectivelmin e o o s as w n mpon nts o 3- parts to 9 parts fumaric acid and 1 part to 4 parts of boric acid, and not more than 32,000 parts of water, contribute an effective portion of the perservative result.

,8- A ba s ati n un cid Qll tiQQ 91 in e ie d m o i i w re n. inrnaric acid, sodium benzoate and boric acid present, respectively, in the proportions as between components of 3.5 parts to 9 parts fumaric acid, 4 parts to 8 parts sodium benzoate, and 1 part to 4 parts b-oric acid, and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

29. A bacteriostatic and fungicidal solution for retarding organic decomposition wherein furnaric acid and sodium benzoate present, respectively, in the proportions as betweencomponents of 8 parts fumaric acid, 8 parts sodium benzoate and not more. than 32,000 parts of water, contribute an effective portion of the preservative result.

30. As an article of manufacture, the composi-. tion of matter consisting of a solution of fumario acid 3.5 parts to 9 parts, sodium benzoate 4, parts to 8 parts, and not more than 32,000 parts of water.

31. As an article of manufacture, the composition of matter consisting of a solution. of fumaric acid 3.5 parts to 9 parts, boric acid 1 part to 4 parts, and not more than 3 2,000parts of Water.

32. As an article of manufacture, the composition of matter consisting of a solution of fumaric acid 3.5 parts to ,9 parts, sodium benzoate 4 parts a to 8 parts, boric acid 1 part to 4 parts, and, not more than 32,000, parts of water,

33. As an article of manufacture, the composition of matter consisting of a solution of funiaric acid 8 parts, sodium benzoate 8 parts, and not more than 32,000 parts of water.

34, As a bacteriostatic and fungicidal article of manufacture for retarding organic dgcompoi tion wherein fumaric acid and sodium benzoate present, respectively, in the proportions as between components of 3.5 parts to 9 parts and 4 parts to 8 parts to be dissolved in not more than 32,000 parts of water.

35. As a bacteriostatic and fungicidal article of manufacture for retarding organic decomposi-. tion, the composition consisting of 3.5 parts to 9 parts of fumaric acid and 4 parts, to 8 parts sodium benzoate t be s lve n not more than 312,000 parts of water.

Ai e ics a c nd un icidal solution tor retarding decomposition of shell fish wherein iii-.- maric acid and sodium benzoate, respectively, present in the proportions as between components of 3.5 parts to 9 parts not more than 32,000 parts of water, contribute an effective portion of the preservative result.

- 37. A bacteriostatic and fungicidal solution for retarding decomposition of shell fish wherein fumaric acid and sodium benzoate, respectively, present in the proportions as between components of 8 parts and 8 parts, and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

38. The method of retarding decomposition of shell fish comprising treating the same with a bacteriostatic and fungicidal solution in which fumaric acid, sodium benzoate andboric acid, respectively, present in the proportions as between the components of 3.5 parts to 9 parts of fumaric acid, 4 parts to 8 parts of sodium benzoate, and 1 part to 4 parts of boric acid, and not more than 32,000 parts of water, contribute an effective portion of the preservative result. I 39. The method of retarding decomposition of shell fish comprising treating the same with a bacteriostatic and fungicidal solution in which fumaric acid and sodium benzoate, respectively, present in the proportions as between components of 3.5 parts to 9 partsfumaric acid and 4 parts to 8 parts sodium benzoate, and not more than 32,000 parts of water, contribute an effective portion of the preservative result.

40. A a bacteriostatic and fungicidal article of manufacture for retarding organic decomposition wherein are present by weight not less than 3.5 parts of fumaric acid, not less than 4 parts of sodium benzoate, and not more than 32,000 parts of water, and which contribute an effective portion of the preservative result. 41. As a bacteriostatic and fungicidal article of manufacture for retarding organic decomposition wherein are present by weight not less than 3.5 parts of fumaric acid, not less than 1 part of boric acid, and not more than 32,000 parts of water, and which contribute an effective portion of the preservative result.

42. As a bacteriostatic and fungicidal article of manufacture for retarding organic decomposition wherein are present by Weight not less than 3.5 parts of fumaric acid, not less than 1.0 parts of boric acid, not less than 4 parts of sodium benzoate, and not more than 32,000 parts of water, and which contribute an effective portion of the preservative result.

43. The method of retarding decomposition of fruit juices comprising dissolving in said fruit juices fumaric acid and sodium benzoate, said components being present by weight not less than 3.5 parts of fumaric acid, not less than 4 parts of sodium benzoate, and not more than 32,000 parts of said juices.

44. The method of retarding decomposition of fruit juices comprising dissolving in said fruit uices fumaric acid and sodium benzoate, said components being present in not less than the following proportions by weight of 8 parts of fumaric acid, 8 parts of sodium benzoate, and not more than 32,000 parts of said juices.

45. The method of retarding decomposition of citrus products comprising treating citrus products with a bacteriostatic and fungicidal solution formed of fumaric acid and sodium benzoate dissolved in water in the proportions of 3.5 parts to 9 parts of fumaric acid and 4 parts to 8 parts of sodium benzoate in not more than 32.000 parts. of water.

and 4 parts to 8 parts, and

46. The method of retarding decomposition of citrus products comprising treating citrus'products with a bacteriostatic and fungicidal solution formed. of fumaric acid and sodium benzoate dissolved in water in the following proportions of 8 parts of fumaric acid and 8 parts of sodium benzoate in not more that 32,000 parts of water.

47. The methodof retarding decomposition of citrus products comprising treating citrus products with a bacteriostatic and fungicidal solution wherein. are present by weight not less than 3.5 parts of fumaric acid, not less than 4 parts of'sodium benzoate, and not more than 32,000 parts of water, and whichcontribute an effective portion of the preservative result.

48. The method of retarding decomposition of shell fish comprising treating shell fish with ice prepared from a bacteriostatic and fungicidal solution wherein fumaric acid and sodium benzoate respectively are present by weight in the proportions as between said components of 8 parts and 8 parts, and not more than 32,000 parts of water and which contribute an effective portion of the preservative result.

7 49. The method of retarding decomposition of shell fish comprising treating shell fish with ice prepared from a bacteriostatic and fungicidal solution wherein fumaric acid and sodium benzoate respectively arerpresent by weight in the proportions as between said components of 3.5 parts to 9 parts fumaric acid and 4 parts to 8 parts of sodium benzoate, and not more than 32,000 parts of water and which contribute an effective portion of the preservative result.

50. The method of retarding decomposition of shell fish comprising treating shell fish with a bacteriostatic and fungicidal solution whereinv fumaric acid and sodium benzoate are present by-weight not less than 3.5 parts of fumaric acid, not, less than 4 parts of sodium benzoate, and not more than 32,000 parts of Water, and which contribute an effective portion of the preservative result.

51. As an article of manufacture the composition of matter comprising 3.5 to 9 parts of fumaric acid, 1 to 4 parts of boric acid and 4 to 8 parts of sodium benzoate to be dissolved in not more than 32,000 parts of water.

52. As an article of manufacture the composition of matter comprising not less than 3.5 parts of fumaric acid and not less than one part of boric acid and not less than 4 parts of sodium benzoate to be dissolved in not more than 32,000 parts of water.

.53. As an article of manufacture the composi tion of matter comprising not less than 3.5 parts of fumaric .acid and not less than 4 parts of s odiumbenzoate to be dissolved in notmore than 32,000 parts of water.

54. As an article of manufacture the composition of matter comprising not less than 3.5 parts of fumaric acid and not less than one part of boric acid to be dissolved in not more than 32,000 parts of water.

55. As an article of manufacture the composition of matter consisting of not less than 3.5 parts of fumaric acid and not less than 4 parts of sodium benzoate to be dissolved in not more than 32,000 parts of water.

. LAWRENCE FRANDSEN.

No references cited. 

1. A BACTERIOSTATIC FUNGICIDAL SOLUTION FOR RETARDING DECOMPOSITION OF FOOD WHEREIN FUMARIC ACID, BORIC ACID, AND SODIUM BENZOATE, RESPECTIVELY, PRESENT IN THE PROPORTIONS AS BETWEEN THE COMPONENTS OF 7.5 PARTS TO 9 PARTS OF FUMARIC ACID, 6.0 PARTS OF SODIUM BENZOATE, AND 2.5 PARTS BORIC ACID, AND NOT MORE THAN 32.000 PARTS OF WATER, CONTRIBUTED AN EFFECTIVE PORTION OF THE PRESERVATIVE RESULT. 